Method for producing a dispersion containing silver nanoparticles and use of a mixture containing silver nanoparticles as a coating agent

Process for the production of a silver manoparticle

Dispersion and use of a mixture containing silver manoparticles as a coating agent

TECHNICAL FIELD The invention relates to a coating material with a disperse formulation containing silver manoparticles and to processes for their production and their use, in particular as a coating agent.

State of the art

The biocidal effects of silver are well known. In the medical field in particular in the case of implants, attempts are increasingly being made to reduce the use of antibiotics or to do without the use of antibiotics altogether.

Silver is an effective alternative.

It has long been problematic that added silver particles, especially with bone cement, do not achieve a sufficient effect. It is believed that this has to do with the usually too small specific surface of the material used.

1

CONFIRMATION COPY Bone cement is usually a

Material due to a polymerization reaction

hardens. Is known in practice, for example

Bone cement based on methyl methacrylate. This usually consists of two components, namely a liquid and a solid component. The solid component can comprise a largely polymerized polymer, as well as a polymerization initiator and other components via which, for example, the reaction rate is adjusted. The monomer component comprises a monomer or a prepolymer, via which, after mixing, the

Liquid component with the solid component one

Polymerization reaction is set in motion, due to which the initially pasty mass turns into a solid

hardens. Bone cement is used, for example, for the

Use of endoprostheses, for the production of spacers, for multi-part prostheses and for vertebro and

Kyphoplasty used. Depending on the desired application, bone cements with different

Strength properties and curing properties are provided.

To provide an antibiotic effect, it is known to add an antibiotic such as gentamicin.

Even with bone cement and polymer-based

Coating materials would be desirable, in addition or as an alternative to achieving silver

add antimicrobial effect.

Because of the special properties, in particular the larger specific surface area, it would be particularly desirable to add nanoparticulate silver. An addition of nanoparticulate silver to the solid component usually fails because one

Provision of nanoparticulate silver in solid

Condition would hardly be possible as this agglomerates.

The addition of silver in the liquid phase is also

difficult, because on the one hand there are agglomeration effects, and furthermore it has not been possible to provide a sufficiently stable dispersion with nanoparticulate silver, which remains dispersed even in non-polar or in non-polar liquids such as methyl methacrylate. According to a general definition, "nanoparticles" is a designation for particles which have a size in the range less than 100 nm. The use of the prefix "Nano" represents, according to the official

Definition according to ISO TC 229, a differentiation from particles in the sub-micrometer range (> 100 nm). In general, it can be assumed that substances that are referred to as nanomaterial changed chemical and physical

Possess properties. In the case of nanometals, for example, gold and silver show different colors than the corresponding metals, namely red and yellow.

It is also scientifically proven that

Nanoparticles of a substance have an increased surface energy. The smaller the particles are, the higher their surface energy is. As a consequence

Nanoparticles are generally to be regarded as unstable because their high surface energy means that they easily react to form new compounds or larger, more stable aggregates. For the example of nanometals, this means that even the particles of noble metals can also quickly

Oxidize atmospheric oxygen as soon as the size of the particles is in the range of nanometers.

Technologically usable nanoparticles can only be obtained if their surfaces are chemically or physically protected and thus stabilized. Nanoparticles can be described as "technologically usable"

Manufacture, processing and application, keeping or preserving their original particle size.

Possibilities of stabilizing nanoparticles in

Dispersions are known from the prior art. There are three main processes for the production of metallic nanoparticles. In a first process, the nanoparticles are supported on solids for stabilization. The solids are always in a stable size in the micrometer range. A disadvantage of using the products produced in this way is on the one hand the loss of the nanoscale and on the other hand the high filler load. The filler used, which serves as the basis for the formation of the metal nanoparticles, has grain sizes in the range of micrometers and is completely unsuitable, for example, for the production of thin structures or fibers. In practice, the

Percentage by weight of the filler

Nanometal component.

In flame-pyrolytic processes, the cluster consisting of micro and nanoparticles is obtained as a solid, which has to be redispersed for further use, which is often no longer completely possible due to storage influences. In addition, the

Distribution of the nanoparticles never take place optimally, since it can only be as good as the distribution of the

Microparticles on which they are deposited.

A second process is the synthesis of

Metal nanoparticles through stabilization by means of polymers such as polyvinylpyrrolidone in the polyol process, which is often described in the literature as a standard method.

However, only a few are here

Metal nanoparticle concentrations reached (range less than 0.1% by weight of silver). The third variant for producing metal nanoparticles is a PVD process (Physical Vapor Deposition), in which the underlying metal is evaporated. To

Stabilization of the nanoparticles produced in this way

again polymers or silicones used. The generation of metal vapor is a very energy-intensive process that requires evacuated process chambers. This

Manufacturing processes are therefore uneconomical. In addition, the polymers and silicones used pose considerable technical problems in further processing, since redispersion is often impossible.

In addition, DE 10 2006 056 284 A1 describes the production of an antimicrobial aqueous dispersion by mixing an aqueous dispersion of nanoscale particles which has at least one antimicrobial metal

included with an aqueous dispersion of a

Polymerization, polycondensation or

Polyaddition product known. The silver nanoparticles are produced by chemical reduction in water. Sodium chloride is used to stabilize the silver nanoparticles. A disadvantage that all production variants show is the poor processability of the metal nanoparticles in polymer melts, for example when additives are added to thermoplastic polymers. Solids cannot be incorporated homogeneously without prior dispersion.

There is therefore still a need for stable ones

Dispersions of silver nanoparticles with antimicrobial properties.

Presentation of the invention

The object of the invention, as characterized in the claims, is to provide stable dispersions of silver nanoparticles which, however, can also be used in particular in bone cement or as an antibacterial coating for implants and medical devices. In particular, the dispersion is polymer-based

Bone cements and coating materials used.

The object of the invention is already achieved by a method for producing a silver nanoparticle-containing

Dispersion, solved by a dispersion containing silver nanoparticles and by using a mixture containing silver nanoparticles according to one of the independent claims. Further advantageous details, aspects and configurations of the present invention result from the dependent claims, the description, the examples and the

Characters.

The invention relates on the one hand to a method for

Production of a dispersion containing silver nanoparticles. This dispersion is intended in particular for the production of bone cement or for a coating agent,

especially used for implants and medical instruments. Further use is as

Antibacterial carrier material is intended both in the medical field and for clothing and everyday objects.

According to the invention, a silver salt and a

Stabilizer provided.

A reducing agent and an organic polymerizable solvent are further provided. As

are organic polymerizable solvent

in particular polymers or prepolymers are provided which can then be used, for example, as a coating agent or as a component of a bone cement.

A solution is made from silver salt, stabilizer and reducing agent.

After the solution has been prepared, a base and an inorganic salt are added.

With the addition of the base, nanoparticles precipitate, which

disperse. About the inorganic salt that becomes in the solution

remaining water hydrated. An aqueous phase now forms, whereas the silver nanoparticles predominantly remain in the organic polymerizable solvent due to the added stabilizer. The aqueous phase can now be separated off, for example decanted, so that a polymerizable one

organic solvent with silver nanoparticles

remains.

The invention thus essentially

anhydrous monomer containing silver nanoparticles or

Prepolymer can be provided, for example a

Acrylate, especially methyl methacrylate or butyl acrylate.

It goes without saying that a certain proportion of water can remain in the organic solvent, since small amounts of water are soluble, for example, in methyl methacrylate.

But it remains essentially organic

polymerizable solution back, which for example as a coating material or as a component of one

polymerizable material, especially bone cement can be used.

The invention further relates to a

Dispersion containing silver nanoparticles, which is used in particular as bone cement, antibacterial carrier material or coating agent. The dispersion containing silver nanoparticles comprises

Silver nanoparticles, at least one stabilizer and at least one wetting and dispersing additive, the

Silver nanoparticles are dispersed in a liquid monomer, prepolymer or polymer.

The invention is based on the knowledge that a stabilizer and a further network and

Dispersing additive it is possible to provide a dispersion in an organic liquid, for example an acrylate with silver nanoparticles, which is stable over a long period of time.

The stabilizer is preferably selected from the group consisting of polyoxyethylene monoalkyl acid ester,

Polyoxypropylene monoalkyl acid esters, polyoxyethylene di alkyl acid esters, polyoxypropylene di alkyl acid esters,

Polyoxyethylene 1ri alkyl acid esters, polyosypropylene ri alkyl acid esters and mixtures thereof.

A nonionic surfactant, in particular an organosilicon surfactant, is preferably used as the wetting and dispersing additive. The inventors suspect that nanoparticles from the

Stabilizer and then coated as a second layer by the wetting and dispersing agent.

While the stabilizer especially in a first

If the manufacturing step serves to ensure that nanoparticles precipitate in an aqueous solution and do not agglomerate, the wetting and dispersing additive ensures that the nanoparticles also remain dispersed in a less polar organic liquid. The

Dispersion containing silver nanoparticles can be used, for example, as a monomer, in particular for the production of

Bone cement, for a coating solution or as

Additive for polymer materials can be used.

In particular, an acrylate or an acrylate precursor, in particular methyl methacrylate, is used as the polymer. A mixture containing silver nanoparticles, comprising silver nanoparticles and at least one stabilizer, is preferably used for the present invention

selected from the group consisting of polyoxyethylene monoalkyl acid esters, polyoxypropylene mono alkyl acid esters, polyoxyethylene di alkyl acid esters, polyoxypropylene di alkyl acid esters, polyoxyethylene tri alkyl acid esters and polyoxypropylene tri alkyl acid esters.

This mixture, which for the invention

Bone cement or the coating agent is used, will be described in detail below.

In the present text, all statements of proportions in% by weight relate to the weight of the total

Formulation as a 100% basis.

The mixture used contains at least one

Stabilizer selected from the group consisting of

Polyoxyethylene monoalkyl acid esters, polyoxypropylene monoalkyl acid esters, polyoxyethylene di alkyl acid esters,

Polyoxypropylene-di-alkyl acid esters, polyoxyethylene-tri-alkyl acid esters and polyoxypropylene-tri-alkyl acid esters. These stabilizers are compounds with surface-active properties from the group of nonionic surfactants, which are in liquid form at room temperature. Nonionic surfactants in the sense of

Invention are surface-active chemical components that combine uncharged polar and non-polar regions

Have molecule. In addition, nonionic surfactants have no dissociable functional groups.

A mixture according to the invention containing silver nanoparticles contains dispersion-stabilized silver nanoparticles which cannot aggregate into larger agglomerates, since the stabilizers used are liquid in the temperature range from 0-240 ° C. In contrast, the state of the

Technology, for example, many silver nanoparticle products, which are offered as dry powders, but which due to their tendency to agglomerate during transport and storage for dispersion in organic solvents, such as methyl methacrylate, only with a high degree of mechanical strength

Energy input and then only incomplete

can be redispersed.

Combinations of surfactants are particularly preferred for use in the present invention

Components from the aforementioned chemical classes. According to a particularly preferred embodiment, at least two stabilizers are therefore present in the mixture.

If several stabilizers are present, these can be different stabilizers of one of the classes of chemical compounds mentioned or stabilizers of different classes of compounds. With a combination of three different stabilizers you can

For example, three different polyoxyethylene monoalkyl acid esters can be used, but it can

for example, two different polyoxyethylene monoalkyl acid esters and a polyoxypropylene monoalkyl acid ester or, for example, a polyoxypropylene di alkyl acid ester, a polyoxyethylene tri alkyl acid ester and a polyoxypropylene tri alkyl acid ester. Any combination of these nonionic surfactants is possible. The mixture of stabilizers particularly preferably consists of a combination of nonionic surfactants from two different of the compound classes mentioned above.

According to a particularly preferred embodiment, the stabilizer or stabilizers are selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,

Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene glyceryl trioleate, polyoxyethylene glyceryl monolaurate, polyoxyethylene glyceryl monooleate,

Polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monoricinoleate, castor oil, hydrogenated castor oil and soybean oil1.

The stabilizers are often not below theirs

Chemical names known but under their respective trade names. Stabilizers preferred in the context of the present invention are Tween20 ™, Tween40 ™,

Tween60 ™, Tween80 ™, Polysorbat ™, Tagat TO ™, Tagat TO V ™, Tagat L2 ™, Tagat S2 ™, Tagat R40 ™, Triton X 100 ™, Hydrogenated Castoroil ™, PEG 20 Glyceryl Stearate ™, PEG 20 Glyceryl Laurate ™, PEG 40 Castoroil ™, PEG 25 Glyceryl Trioleate ™, Newcol, Montane ™, Lonzest ™,

Liposorb ™, Nonion ™, Kuplur ™, Ionet ™, Kemotan ™,

Grillosan ™, Ethylan ™, Glycomul ™, Emsorb ™, Disponil Amisol ™, Armotan ™, Sorbax ™, Sorbitan ™, Span ™ and

This list of stabilizers is not complete, as different manufacturers market the same or similar products under different names or new nonionic surfactants of the above-mentioned classes of compounds in the

Be synthesized in the future and also in one

mixture according to the invention can be used.

There are at least two stabilizers in the mixture

contained, so these are preferably in one

Quantity ratio in the range of 1: 1 to 2: 1 present in the mixture.

Since the nonionic surfactants contained in the mixture act as stabilizers for the nanometal formed, there is a quantitative relationship between the concentrations of the stabilizer and the metal. According to a further preferred embodiment, the quantitative ratio of silver nanoparticles to stabilizer is in the range from 10: 2 to 10:50, particularly preferably in the range from 10: 5 to 10:10. If several stabilizers are present, the "metal to stabilizer ratio" is the "metal ratio to the total of those present"

Stabilizers "to understand. When using the

preferred quantitative ratios, mixtures are obtained from which particularly stable dispersions of

Metal nanoparticles can be produced, which can be used universally. The metal nanoparticles preferably have a particle size of 1 to 100 nm, particularly preferably 1 to 50 nm,

particularly preferably 1 to 20 nm. The present invention also relates to a formulation comprising a silver nanoparticle

Dispersion of one of those described above

mixtures containing metal nanoparticles. The formulation according to the invention is liquid and does not otherwise contain any solid secondary components which would restrict the possibilities for further use.

In the mixture according to the invention as well as in the

Formulation according to the invention are one or more surface-active components as stabilizers

included, in addition to stabilizing the

Silver nanoparticles also enable further processing (by repeated dispersion, emulsification) in all other substrates. The most technologically demanding further processing is the processing in

thermoplastics. The temperatures used here range up to 300 ° C. Up to this temperature, it is desirable that the formulation used for the additives is liquid, which is achieved by using one or more surface-active components which are liquid up to a temperature of 300 ° C. for a short time. At least two stabilizers are particularly preferably present in the formulation. If several stabilizers are present, they can be different

Stabilizers of one of the classes mentioned chemical

Trade compounds or stabilizers of different classes of compounds. With a combination of three

Different stabilizers can therefore be used, for example, three different polyoxyethylene monoalkyl acid esters, but it is also possible, for example, to use two different polyoxyethylene monoalkyl acid esters and a polyoxypropylene monoalkyl acid ester or, for example, a polyoxypropylene di alkyl acid ester, a polyoxyethylene tri alkyl acid ester and a polyoxypropylene tri-alkyl acid ester can be used. Any combination of these nonionic surfactants is possible. The mixture of stabilizers particularly preferably consists of a combination of nonionic surfactants from two different of the compound classes mentioned above.

Since the at least one nonionic surfactant is used as a stabilizer for the nanometal formed, there is a quantitative relationship between the concentrations of the

Stabilizer and silver. The invention

Formulation for use, for example, in

Methyl methacrylate has a ratio of silver to stabilizer in the range from 10: 2 to 10: 50.

The metal ratio is preferably too

Stabilizer from 10: 5 to 10: 20, particularly preferably from 10: 6 to 10: 10. Are several stabilizers

when present, the “quantitative ratio of metal to stabilizer” is to be understood as the “quantitative ratio of metal to the total of stabilizers present”. When using the preferred quantitative ratios, particularly stable dispersions of silver nanoparticles are obtained. More than two stabilizers are preferred in the

present formulation according to the invention. In this case, the content of a first stabilizer is in the range from 30 to 90% by weight, preferably between 40 to 60% by weight, particularly preferably between 45 to 55% by weight. Of the

remaining weight percentage up to 100 percent is divided among the others used in combination

Stabilizers according to the invention, which in turn are divided into proportions of 0 to 100 wt .-%. The weight percentages given here relate to the total weight, in deviation from other information

Stabilizers as a 100% basis. One or more stabilizers selected from the group consisting of Tagat TO V ™, Tween20 ™, Tween80 ™ and Tagat L2 ™ are particularly preferably present in the formulation. Particularly stable and universally applicable dispersions are obtained using these stabilizers.

According to a very particularly preferred embodiment of the present invention, the formulation is as

Stabilizer a mixture of Tagat TO V ™ and Tween20 ™ present. Particularly preferred are formulations in which the quantitative ratio Tagat TO V ™ to Tween20 ™ is in the range from 1: 2 to 2: 1 and formulations in which the

Quantity ratio Tagat TO V ™ to Tween20 ™ is approximately 1: 1.

Regarding the particle size, reference is again made to the definition formulated at the beginning, according to which the

Silver nanoparticles have a particle size of less than 100 nm. In the formulation according to the invention, the silver nanoparticles are present in a particle size of 1 to 100 nm, preferably 1 to 50 nm, particularly preferably 1 to 20 nm. The morphology of the silver nanoparticles can have shapes of triangles, cubes, spheres, rods or platelets.

The formulation preferably contains stable, nanoscale metal particles in a concentration of 0.5 to 60% by weight, the quantitative ratio of silver nanoparticles to

Stabilizer in the range from 10: 2 up to 10: 50,

is preferably in the range from 10: 5 to 10:10. In the preferred areas, particularly stable dispersions of silver nanoparticles are obtained which can be used universally.

The silver nanoparticles are particularly preferably present in the formulation in a proportion of 1 to 40% by weight, preferably in a proportion of 5 to 30% by weight.

In principle, the formulation according to the invention can be prepared with any type of solvent, but water is particularly preferably used as the solvent and thus a disperse, aqueous formulation containing silver nanoparticles is produced. The formulation particularly preferably contains at least 70% by weight of water.

As an alternative to water, an organic solvent can be used to prepare the dispersion. It is then a dispersion of one of the silver nanoparticle-containing mixtures described above in an organic solvent. The organic solvent is very particularly preferably

Methyl methacrylate.

The present invention also encompasses a process for the preparation of the disperse formulations containing metal nanoparticles described above, comprising the steps of providing a metal salt, providing at least one stabilizer selected from the group consisting of polyoxyethylene monoalkyl acid esters, polyoxypropylene monoalkyl acid esters, polyoxyethylene di alkyl acid esters , Polyoxypropylene-di-alkyl acid ester, polyoxyethylene-tri-alkyl acid ester, Polyoxypropylene-tri-alkyl acid ester, providing a reducing agent, providing a solvent, preparing a solution of metal salt, stabilizer and reducing agent, adding a base to the solution, the base being added continuously over a period of 5 to 48 hours in such a way that the pH of the

Formulation is between 0 and 6.

A formulation with a very narrow distribution of the

Obtain particle sizes of the nanoparticles. Water or a is preferred as solvent

organic solvent used. It is particularly preferably an aqueous solution, ie a disperse, aqueous formulation containing metal nanoparticles is produced.

The base is preferably added continuously over a period of 9 to 30 hours. In this way, a formulation with a particularly narrow distribution of the particle sizes of the nanoparticles is obtained.

The manufacturing method according to the invention is a

reductive chemical process. Accordingly, the

Silver particles made from their salts by chemical reduction. In general, any chemical or physical reducing agent can be used to produce the silver nanoparticles according to the invention. Physical reducing agents are understood here to mean an increase in temperature or irradiation with light. The use of a chemical is advantageous

Reducing agent, because here material sales of 100 percent and very high reaction rates can be achieved. Surprisingly, it has been shown that in the presence of at least one stabilizer from the group

Polyoxyethylene monoalkyl acid esters, polyoxypropylene monoalkyl acid esters, polyoxyethylene di alkyl acid esters,

Polyoxypropylene-di-alkyl acid esters, polyoxyethylene-tri-alkyl acid esters and polyoxypropylene-tri-alkyl acid esters can be used with very strong reducing agents, which leads to an increased reaction rate without at the same time risk of the formation of a larger proportion of large, undesirable silver particles.

Chemical reducing agents include those

preferred that have no reaction by-products remaining in the reaction mixture, such as the corresponding one

generate oxidized form of the respective reducing agent, which the quality of the silver nanoparticle-containing

would reduce disperse, aqueous formulation. According to a preferred embodiment, therefore

Reducing agent used, which reacts with the metal ions of the metal salt to form elemental metal and otherwise predominantly gaseous reaction products. Reducing agents which can leave the reaction solution in their oxidized form as a gaseous substance, such as hydrazine hydrate, are particularly preferred.

Of course, the invention

Silver nanoparticles can also be obtained with any other reducing agent.

The reductive production of metals can be formulated as a pair of redox equations. The first

Partial equation is the reduction equation, according to which

Metal cation is reduced from the metal salt to the element metal. The second partial equation describes the

corresponding oxidative process for the oxidation of the reducing agent to the corresponding oxidation product, which ideally leaves the reaction solution in the gaseous state. All reducing agents have in common that a proton is created for each electron transferred. This proton helps keep the pH of the whole

Reaction solution falls very strongly. The decrease in pH is responsible for the reaction

undesirably comes to a standstill. An alkali must therefore be added to trap the protons that slow down the overall reaction. Surprisingly, it was found that the type of lye, the concentration of the lye and the rate at which the lye is added are decisive for the distribution of the particle sizes of the nanoparticles in the formulation produced.

Ammonia, potassium hydrogen carbonate or sodium hydroxide is preferably used as the base. When using these bases, particularly stable dispersions with a narrow distribution of the particle sizes of the nanoparticles are obtained.

The amount of lye added is to be measured so that a pH neutral after the reaction is complete

Dispersion is obtained. The pH is then between pH 5 and pH 9.

Alkaline or proton acceptors are defined by their pK_b Values. The pK_b Value is the negative decadal

Logarithm of the proton concentration in equilibrium and is therefore a measure of the strength of the base.

Bases which have a pK are suitable for producing the formulation according to the invention_b Value in the range from -2 to

10.5, preferably 1.5 to 9.1, particularly preferably in the range 3.5 to 7.5.

In addition to the base strength, the rate of addition to the reaction solution for the preparation of the

formulation according to the invention crucial. If the addition takes place too quickly, the particle size spectrum shifts towards larger particles, which in extreme cases are in the micrometer range. On the other hand, if the addition is too slow, no material yields greater than 90%

obtained because already formed nanometal catalytically causes the degradation of reducing agents and therefore none

There is more reaction partner for the production of silver nanoparticles.

Experiments have shown that the rate of addition of the alkali should be in the range from 9 to 30 hours with a batch size of 50 kg in order to achieve the high quality of silver nanoparticles according to the invention. At

correspondingly smaller batch sizes also reduce the time for adding the lye. It can go up

Addition time can not be extended arbitrarily, since the

catalytic degradation of the reducing agent by nanometal already formed after 48 hours at the latest

Overall yield noticeably affected.

The rate of addition of the alkali is such that the pH of the dispersion is always between 0 and 6. A higher pH value leads to a too fast reaction and thus to uncontrolled particle growth. One too

low pH causes the reaction to

Comes to a standstill and so that no more nanometal is formed.

The formulation according to the invention can be used in a large number of applications, the

various uses clearly advantageous

Properties can be achieved. The metal nanoparticles of the formulation according to the invention or the metal nanoparticles of a formulation produced by the method according to the invention can be used in particular to achieve this

antimicrobial activity can be incorporated into various substrates.

The present invention also relates to a method for the production of bone cement or a coating material for implants or

medical instruments with one of the above closer

described mixtures containing silver nanoparticles, one of those described in more detail above

an inorganic salt is added to formulations containing silver nanoparticles or after carrying out one of the processes described above for producing a

an inorganic salt is added to the silver nanoparticle-containing formulation, the inorganic salt comprising at least one element of the fourth or fifth main group of the Periodic Table of the Elements as a component of the anion.

The present invention thus comprises two variants of methods for producing a mixture containing silver nanoparticles, namely one

- Method of making a

Comprehensive mixture containing silver nanoparticles

Silver nanoparticles and at least one stabilizer selected from the group consisting of polyoxyethylene mono-alkyl acid esters, polyoxypropylene mono-alkyl acid esters, polyoxyethylene di-alkyl acid esters, polyoxypropylene di-alkyl acid esters, polyoxyethylene tri-alkyl acid esters and polyoxypropylene tri-alkyl acid esters, being one Formulation containing silver nanoparticles comprising a dispersion of a

Comprehensive mixture containing silver nanoparticles

Silver nanoparticles and at least one stabilizer selected from the group consisting of polyoxyethylene mono-a1ky1s ureester, polyoxypropylene-monoalkyl acid esters, polyoxyethylene di-alkyl acid esters, polyoxypropylene di-alkyl acid esters, polyoxyethylene tri alkyl acid esters and polyoxypropylene tri alkyl acid esters, an inorganic salt is added where

inorganic salt comprises at least one element of the fourth or fifth main group of the Periodic Table of the Elements as a component of the anion

Process for producing a

Compound containing silver nanoparticles

Silver nanoparticles and at least one stabilizer selected from the group consisting of polyoxyethylene mono-alkyl acid esters, polyoxypropylene mono-alkyl acid esters, polyoxyethylene di-alkyl acid esters, polyoxypropylene di-alkyl acid esters, polyoxyethylene tri-alkyl acid esters and polyoxypropylene tri-alkyl acid esters, comprising the steps

- provision of a silver salt,

- Providing at least one stabilizer selected from the group consisting of polyoxyethylene monoalkyl acid ester, polyoxypropylene monoalkyl acid ester, polyoxyethylene di alkyl acid ester, polyoxypropylene di alkyl acid ester, polyoxyethylene tri alkyl acid ester, polyoxypropylene tri alkyl acid ester and their

Mixtures,

Provision of a reducing agent,

- providing a solvent,

- preparation of a solution of silver salt, stabilizer and reducing agent,

Adding a base to the solution, the base being added continuously over a period of 5 to 48 hours in such a way that the pH of the formulation is between 0 and 6,

- Add an inorganic salt, which

inorganic salt comprises at least one element of the fourth or fifth main group of the Periodic Table of the Elements as part of the anion. A mixture of nanoparticles according to the invention can thus be obtained from a corresponding formulation containing nanoparticles by adding an inorganic salt. It is irrelevant whether the

formulation containing nanoparticles was prepared by dispersing a mixture containing nanoparticles or whether the formulation containing nanoparticles was obtained by reducing a silver salt in solution. In particular in the production of the nanoparticle-containing mixture from a nanoparticle-containing formulation, which was obtained by reducing a silver salt in solution, the addition of an inorganic salt is associated with very special advantages. Because it was

Surprisingly found that the addition of inorganic salts separates the dispersion obtained by adding a base to the solution of silver salt, stabilizer and reducing agent into two chemical phases 1 and 2. Phase 1 contains the silver nanoparticles in the liquid stabilizer mixture used. The

Solvents, the inorganic salts and the by-product ammonium nitrate are in phase 2 above phase 1. The two phases can now be separated from one another in a simple manner by decanting the upper phase 2. What remains is phase 1, which only consists of the silver nanoparticles and the liquid stabilizers.

The ones in the form of a dispersion

In this way, silver nanoparticles, which generally have particle sizes of 1-20 nm and are chemically stabilized, are separated from those contained in the dispersion

By-product ammonium nitrate and the solvent used, in particular water, separated. The silver nanoparticulate formulations according to the invention can thereby be made accessible to additional application fields. These fields of application include

Applications in which the solvent used and the by-product interfere with ammonium nitrate. In particular, water and ammonium nitrate are used in applications with polar or aprotic solvents to disperse the

stabilized silver nanoparticles.

Particularly good results are achieved if the solvent is water and the inorganic

Salts are water-soluble inorganic salts. In this case, by adding water-soluble inorganic salts, adding a base to the solution of

Metal salt, stabilizer and reducing agent dispersion obtained in two chemical phases 1 and 2 separately. Phase 1 again contains the silver nanoparticles in the

used liquid stabilizer mixture. The

Solvent water, the water-soluble salts and that

By-product ammonium nitrate is in phase 2 above phase 1. The two phases can be separated by decanting off the upper aqueous phase 2. What remains is phase 1, which only consists of the

Silver nanoparticles and the liquid stabilizers.

For more detailed characterization of suitable salts, their cationic and anionic constituents must be separated

to be viewed as. Salts generally consist of at least one cation and at least one anion. An undesirable interaction of cations with the stabilized one

Formulation containing metal nanoparticles is not to be expected since the silver used is present either as an uncharged metal or as a positively charged cation.

If water is used as the solvent, then the

Selection of the suitable cations / anions combinations in the form of suitable salts based on the idea that the phase separation is caused by the stress on the hydration ability of the water by charged ions. The ability to hydrate is expressed by the ability to form hydrogen bonds. It is also the reason for the stability of the dispersion in the

Dispersion medium water. This means that there is a certain amount of competition between the stabilizers enveloping the silver nanoparticles and the dissolved reaction by-products such as ammonium nitrate.

The stabilizers used according to the invention are nonionic macromolecules that

are only connected to the water molecules by weak dipole-dipole interactions. The addition of

Salting therefore intends to remove the stabilizing influence of the hydrogen bonds on the total dispersion by using electrically charged ions which have much stronger interactions with the water dipoles.

be introduced. As a rule, the degree of interaction with water is of the ionic radius and of that

Ion charge depending on the form that the

Interaction with decreasing ion radii and increasing ion charge increases. When selecting suitable salts, their solubility in water is also important. With

increasing solubility of the salts in water also reduces the formation of interaction forces with the

Water molecules too. The choice of anions is also limited by the fact that undesired interactions with existing silver cations have to be avoided. With that everyone divorces

Anions from which form poorly soluble compounds with the silver used, e.g. halides, chalcogenides and their oxygen compounds.

The inorganic salt therefore particularly preferably comprises at least one element of the fifth main group of

Periodic table of the elements as part of the anion, with particular preference being given to the inorganic salt

Includes nitrogen as part of the anion. It is particularly preferred that the phase formed after adding the inorganic salt is then decanted from the silver nanoparticle-containing phase, which essentially consists of silver nanoparticles and stabilizers

Mixture.

The present invention also relates to a method of making one of the above

formulations described containing silver nanoparticles comprising the steps of providing one of the mixtures containing silver nanoparticles described in more detail above,

Provide a solvent, add the

mixture containing silver nanoparticles to the solvent.

The present invention thus comprises a method for producing a formulation containing silver nanoparticles, comprising a dispersion of a mixture containing silver nanoparticles, comprising silver nanoparticles and at least one stabilizer selected from the group consisting of polyoxyethylene monoalkyl acid esters, polyoxypropylene monoalkyl acid esters, polyoxyethylene di alkyl acid esters,

Polyoxypropylene-di-alkyl acid esters, polyoxyethylene-tri-alkyl acid esters and polyoxypropylene-tri-alkyl acid esters comprising the steps of providing one

Compound containing silver nanoparticles

Silver nanoparticles and at least one stabilizer

selected from the group consisting of polyoxyethylene mono-alkyl acid esters, polyoxypropylene mono-alkyl acid esters, polyoxyethylene di-alkyl acid esters, polyoxypropylene di-alkyl acid esters, polyoxyethylene tri-alkyl acid esters and polyoxypropylene tri-alkyl acid esters, providing a solvent, adding the silver nanoparticle-containing

Mix to the solvent.

The chemically stabilized according to the invention

Silver nanoparticles can be wetted or dissolved by the solvent without losing the stabilizer shell necessary for stabilization.

The solvent is preferably water or an organic solvent. All organic, protic, aprotic, polar and non-polar compounds or mixtures thereof can be used.

According to a particularly preferred embodiment of the present invention, at least one wetting and dispersing additive is additionally added. The network and

Dispersing agents ensure wetting or

Solution of the silver nanoparticles by the used

Solvent. Suitable chemical compounds that act as wetting and

Dispersing additives can be used

Alkylphenol ethoxylates, amino-functional polyesters, phosphorus-containing substances such as, for example, organically modified phosphates, phosphonates,

Polyphosphorus compounds and alkylphosphonates, or a mixture of these compounds.

The network and

Dispersing additive around an organically modified phosphate, a phosphonate, a polyphosphorus compound

Alkyl phosphonate, a phosphorus compound with mixed organic ligands, an oligomer or a polymer with phosphate-containing ligands.

Such wetting and dispersing additives are offered by Evonic, BYK Chemie and Ciba Geigy.

The chemically stabilized silver nanoparticles with a preferred particle size of 1-20 nm can thus, with the aid of wetting and dispersing additives, inter alia in organic solvents, in particular in

Methyl methacrylate, can be incorporated. This incorporation can be carried out using the simplest stirring or mixing techniques, since the metal nanoparticles are redispersed by the

Use of the stabilizers according to the invention is not necessary. This way they become stable

Dispersions of, for example, silver nanoparticles with a particle size of preferably less than 20 nm in

organic solvents, preferably in methyl methacrylate, in a concentration of 5,000 mg / kg to 50,000 mg / kg silver content. The invention particularly relates to a bone cement, an antibacterial carrier material or a

Coating agent, in particular an acrylate-based coating agent, which with the above

described method can be produced.

The invention further relates to a bone cement, an antibacterial carrier material or a

Coating agents for implants or medical

Devices comprising silver nanoparticles.

The coating agent is in particular a

Liquid coating agent, for example an acrylate or silicone. The coating agent can be applied, for example, by immersion (dip coating).

According to the invention, the nanoparticles are coated with at least a first and a second stabilizer and dispersed in a polymer.

A polymer is any form of prepolymer as well as an essentially unreacted one

Monomer solution, which predominantly, for example

Includes methyl methacrylate, understood.

The inventors found that through the

Using two different stabilizers,

in particular by using two emulsifiers, it is possible to provide a stable dispersion which is retained even in non-polar liquids.

The. Is particularly suitable as the starting material

Formulation described above, in which one imagines that it already comprises silver nanoparticles with a shell made of at least one stabilizer.

But even with this wording is not always

ensured that it did not fail and

Agglomeration is coming.

However, the inventors have found that by selecting a second stabilizer, which is believed to wrap around the first like a second shell

Stabilizer sets, it is possible to provide a stable dispersion in a non-polar liquid.

A nonionic surfactant, in particular an organosilicon surfactant, is used in particular for this. Such a surfactant is available, for example, under the trade name Tego DISPERS 655.

In particular, the mixture, for example the monomer component of a bone cement or the

Coating solution at least 0.1, preferably at least 0.2% of the second stabilizer added. The goal here is the amount of additional chemical substances

to keep as low as possible.

The inventors have found that an amount of less than 1, preferably less than 0.2%, is sufficient to stabilize nanoparticles with an average particle size between 5 and 50, preferably between 10 and 20 nm.

A dispersion can thus be provided in which at least 90, preferably at least 99% of the silver nanoparticles are smaller than 50, preferably smaller than 20 nm.

The nanoparticles preferably have an essentially spherical shape, a spherical shape in the sense of the invention being understood to mean a shape in which the length, width and height of the particles are less than 20%.

differ from each other, so there is no example

are acicular particles.

In particular with a proportion of silver nanoparticles between 0.5 and 5, preferably between 1 and 3

Weight percent in the polymer can provide polymer-based coatings or bone cements which have an antimicrobial effect and in which the

Use of antibiotics can at least be reduced or even completely dispensed with the use of antibiotics.

The present invention also includes the use of the formulation according to the invention for the surface treatment of implants and medical devices. The particular advantages achieved with this type of use are explained in more detail in the examples below. The present invention particularly includes

Use of the formulation according to the invention for

Manufacture of antimicrobial surfaces. The particular advantages achieved with this type of use are explained in more detail in the examples below.

The present invention also includes the use of the formulation according to the invention in silicones

Coating material. The particular advantages achieved with this type of use are explained in more detail in the examples below.

The present invention also includes the use of the formulation according to the invention in thermoplastic

Plastics, preferably in polypropylene. The particular advantages achieved with this type of use are explained in more detail in the examples below. The present invention also includes the use of the formulation according to the invention in thermosets, preferably the use for the production of PMMA bone cement. The particular advantages achieved with this type of use are explained in more detail in the examples below.

The present invention also includes the use of the formulation according to the invention for the production of PMMA coatings. The particular advantages achieved with this type of use are explained in more detail in the examples below.

BRIEF DESCRIPTION OF THE DRAWINGS Exemplary embodiments are given below to illustrate the invention and to clarify its advantages. These exemplary embodiments will be explained in connection with the drawings. It goes without saying that this information is not intended to limit the invention. Show it

Fig. A UVvis spectrum of a 5,000-fold diluted 1 aqueous solution of an inventive

Formulation;

Fig. Measured particle sizes and calculated curve of

2nd Scanning Electron Microscope (SEM) records.

Fig. Transmission Electron Microscope (TEM) analysis of the

3rd Silver nanoparticles.

Fig. A transmission electron micrograph

4th (TEM) a 5,000-fold diluted aqueous solution of a formulation according to the invention;

Fig. A transmission electron micrograph

6 (TEM) a coated nonwoven / foil laminate;

Fig. The kinetics of killing on the coated

7 Fleece of Figure 6 applied bacteria

(E. coli.);

Fig. A transmission electron micrograph

8th (TEM) of a polyester masterbatch with 6500 mg / kg

Silver;

Fig. Microfiber strands made of PET / PA with 200 mg / kg

9 nanosilver;

Fig. Elution behavior and antimicrobial activity

10th various polyester microfibers. Ways of Carrying Out the Invention

Example 1:

Formulation of nanosilver with hydrazine hydrate, ammonia, Tagat TO V ™ and Tween20

7,000 g of silver nitrate, 1,760 g of Tagat TO V ™, 1,760 g of Tween20 ™ and 512 g of hydrazine hydrate in 28,439 g of deionized water are presented. The solution is stirred for 3 hours. Then 5,000 g of ammonia solution (14%) are continuously added dropwise over a period of 24 hours. The reaction is complete after the addition and provides a dispersion with a silver content of 10.0% by weight. The particle size and distribution is determined using a UVvis spectrum (FIG. 1). The result is a 10 percent nanosilver dispersion with one

Nanosilver particle size from 1-30 nm.

The absorption spectrum is carried out on a 5,000-fold diluted aqueous solution containing 20 ppm nanosilver, which is clear and deep yellow in color. The UVvis spectrum is recorded in the wavelength range from 750 to 350 nm. The measured absorption values ​​provide a peak with a maximum at 410-420 nm and a peak half-width of around 80 nm.

The dispersing properties of the 10 percent dispersion obtained are excellent both in polar and in non-polar solvents, that is to say without additional chemical effort (dispersing aids) or mechanical

Effort (ultrasound, ultraturax, etc.) to get an absolutely clear solution that only has a color caused by the plasmon effect of the silver. FIG. 4 shows a transmission electron micrograph (TE) of the diluted dispersion from example 1. The dark areas visible in FIG. 4 correspond to the nano-silver particles which have a particle size of 1-30 nm.

Example 2:

Formulation of nanosilver with hydrazine hydrate, ammonia and Tagat TO V ™

7,000 g of silver nitrate, 3,520 g of Tagat TO V ™ and 1,331 g of hydrazine sulfate in 27,620 g of deionized are presented

Water. The solution is stirred for 3 hours. Then 5,000 g of ammonia solution (14%) are continuously added dropwise over a period of 24 hours. The reaction is complete after the addition and provides a dispersion with a silver content of 10.0% by weight. The particle size and distribution is determined using a UVvis spectrum

determined. The result is a 10 percent

Nanosilver dispersion obtained with a nanosilver particle size of 1-30 nm.

Example 3:

Formulation of nanosilver with hydrazine sulfate,

Potassium hydrogen carbonate, Tagat TO V ™ and Tween80 ™ are presented 7,000 g of silver nitrate, 2,360 g of Tagat TO V ™, 1,160 g of Tween80 ™ and 1,331 g of hydrazine sulfate in 27,620 g of deionized water. The solution is stirred for 3 hours. Then 5,000 g of potassium hydrogen carbonate solution (1,900 g of KHCO₃) over a period of 30 hours

dripped continuously. The reaction is complete after the addition and provides a dispersion with a silver content of 10.0% by weight. The particle size and

Distribution is determined using a UVvis spectrum (FIG. 1). The result is a 10 percent

Nanosilver dispersion obtained with a nanosilver particle size of 1-30 nm.

Example 4:

Formulation of nanosilver with glucose, sodium hydroxide, Tagat L2 ™ and Tween20 ™ 7,000 g of silver nitrate, 2,360 g of Tagat L2 ™, 1,160 g of Tween20 ™ and 3,708 g of glucose are presented in 25,243 g

deionized water. The solution is stirred for 3 hours. Then 5,000 g of sodium hydroxide solution (760 g of NaOH) are continuously added dropwise over a period of 30 hours. The reaction is after the addition

completed and delivers a dispersion with a

Silver content of 10.0% by weight. The particle size and

Distribution is determined using a UVvis spectrum. The result is a 10 percent nanosilver dispersion with a nanosilver particle size of 1-30 nm.

Example 5:

Formulation of nanocopper with hydrazine hydrate, ammonia, Tagat TO V ™ and Tween20 ™

10,000 g of copper (II) nitrate, 1,760 g of Tagat TO V ™, 1,760 g of Tween20 ™ and 1,090 g of hydrazine hydrate in 14,260 g of deionized water are presented. The solution is for 3

Hours stirred. Then 5,000 g of ammonia solution (14%) are continuously added dropwise over a period of 24 hours. The reaction is after the addition

completed and delivers a dispersion with a

Copper content of 10.0% by weight.

Example 6:

Further processing of the dispersion from Example 1 to

Production of a liquid, water and salt free

Formulation with silver nanoparticles

The aqueous dispersion containing silver nanoparticles obtained in Example 1 is contaminated with the by-product ammonium nitrate. The silver nanoparticles have particle sizes of 1-20 nm and are chemically stabilized. The silver content is 25% by weight. The water content is 366 g and the ammonium nitrate content is 185 g. 1,000 g of this dispersion are placed in a beaker and heated to 45 ° C. with stirring. The separation of the dispersion into two phases is initiated by adding 78 g of potassium nitrate. After the addition and complete dissolution of the potassium nitrate, the heating is removed and the stirrer is switched off. The separation of the phases can be observed after cooling. The upper, clear, aqueous phase 1 is completely decanted off. The remaining phase 2 has a dark brown color with a syrup-like flow property and a weight of 449 g. The stable dispersion is now ready for incorporation into any organic solvent, especially

Methyl methacrylate. An analysis of the aqueous phase 1 shows a salt content of 263 g and a water content of 366 g.

The analysis of phase 2 containing silver shows the following data:

a) Analysis of the total silver content by ashing at 800 ° C gives 250 g of silver. Related to the

Overall formulation, this corresponds to a silver content of 56% by weight.

b) The analysis of the particle size distribution of the silver obtained is shown in FIG. 1. The determination is carried out by measuring the UVvis absorption spectrum in the wavelength range from 700 nm to 350 nm. The peak maximum at 415 nm corresponds to a particle size of 10 nm. The peak half-width of 80 nm is a measure of the narrow particle size distribution. The correlation with the SEM (Scanning Electron Microscope) and the TEM

(Transmission Electron Microscope) Analyzes, as shown in Figure 2 and Figure 3, allows the specification of the

Particle size distribution of D 100 <20 nm (100% of the

Particle diameters are smaller than 20 nm).

Example 7:

Further processing of the dispersion from Example 1 to

Production of a liquid, water and salt free

Formulation with silver nanoparticles

The aqueous dispersion containing silver nanoparticles obtained in Example 1 is contaminated with the by-product ammonium nitrate. The silver nanoparticles have particle sizes of 1-20 nm and are chemically stabilized. The silver content is 10% by weight. The water content is 746 g and the ammonium nitrate content is 74 g. The separation of the dispersion into two phases is initiated by adding 202 g of potassium nitrate. After the addition and complete dissolution of the potassium nitrate, the heating is removed and the stirrer is switched off. The separation of the phases can be observed after cooling. The upper, clear, aqueous phase 1 is completely decanted off. The remaining phase 2 has a dark brown color with a syrup-like flow property and a weight of 180 g. The stable dispersion is now ready for incorporation into any organic solvent, especially methyl methacrylate.

An analysis of the aqueous phase 1 shows a salt content of 276 g and a water content of 746 g.

The analysis of phase 2 containing silver shows the following data:

a) Analysis of the total silver content by ashing at 800 ° C gives 100 g of silver. Related to the

Overall formulation, this corresponds to a silver content of

55 % By weight.

b) The analysis of the particle size distribution of the

obtained silver is shown in Figure 1. The determination is made by measuring the UVvis absorption spectrum in the wavelength range of 700 nm -

350 nm. The peak maximum at 415 nm corresponds to one

Particle size of 10 nm. The peak half width of maximum 80 nm is a measure of the narrow

Particle size distribution. The correlation with the SEM (Scanning Electron Microscope) and the TEM (Transmission

Electron Microscope) Analyzes, as shown in Figure 2 and Figure 3, allows the specification of the particle size distribution of D 100 <20 nm (100% of the particle diameter are less than 20 nm).

Example 8:

Use of the formulation according to the invention for

Surface treatment of wood

The dispersion according to the invention from Example 1 is used in a concentration of 100 mg / kg (based on the

Silver content in the finished product), as known from the prior art, incorporated into commercially available linseed oil. A stable nanoparticle dispersion is obtained which is suitable for the surface treatment of wood.

The wood treated with the additive wood oil is resistant to a variety of chemicals and water. In addition, the wooden surfaces are protected from colonization by microorganisms, which means that applied microbes on the surfaces described die faster than surfaces with non-additive wood oil.

Example 9:

Use of the formulation according to the invention for

Promotion of plant growth

The dispersion from Example 1 is distributed in water in a concentration of preferably 1-100 µg / kg (based on the silver content in the finished product). A stable nanoparticle dispersion is obtained, which is used for

Growth promotion on plants can be used. The effect of the aqueous nanosilver dispersion on plant growth was determined by means of an algae cultivation test with Scenedesmus sp. examined. The results of the experiment are shown in FIG. 5. In Figure 5, the test duration is on the abscissa

applied nanosilver addition. The optical density (OD) of the culture at 510 nm wavelength, which is proportional to the biomass concentration (algae concentration), is plotted on the ordinate. Cultures without addition of nanosilver (□: 0 ppb nAg) and cultures with different nanosilver contents (0: 1 ppb, ·: 10 ppb, ▲: 100 ppb and ■: 1000 ppb) were examined with regard to algae growth. As can be seen from Figure 5, the algae grow without

Nanosilver addition exponentially in the first 42 hours of cultivation up to an OD of about 2.5. After that, growth stops. The OD of the non-additive

Culture stagnates at around 3. The growth curve of the culture additized with 1 μg / kg nanosilver shows a course analogous to that of the non-additized culture for the first 42 hours of the experiment. While the growth of not

additive culture between 42 hours and

When the end of the experiment almost comes to a standstill at 75 hours, the cultures additized with 1 µg / g nanosilver continue to grow unchecked during this period and reach a final OD value of 4.7.

The algae cultures additized with 10 µg / kg or 100 µg / kg show a significantly higher level after 25 hours compared to the non-additized culture

Algae growth. The algae grow best with a nanosilver addition of 10 ppb. The final value reached after 75 hours of testing is an OD of 5.4. In this experiment, this can be done using a nanosilver

Add 10 µg / kg to Scenedesmus sp. a

Growth growth of 80% compared to one does not

additive algae culture after 75 hours

Demonstrate cultivation time. When 1000 pg / kg of nanosilver is added to the culture, the silver is toxic to the algae. The algae added at the start of the experiment die quickly.

Example 10:

Use of the formulation according to the invention for

Preparation of antimicrobial surfaces The dispersion from Example 1 is preferably used in a concentration of 5-50 g / kg silver

Plasma electrolytic oxidation on metal surfaces, such as titanium coated. Strongly antimicrobially active (R value> 3) surfaces are obtained.

Example 11:

Use of the formulation according to the invention for

Manufacture of coatings for nonwoven / foil laminates

The nanosilver dispersion from example is in a

Concentration of 150 mg / kg (based on the silver content in the coating), as known from the prior art, in a commercially available coating film

certain fluoropolymer dispersion incorporated. A stable, slightly yellow colored dispersion of nanosilver particles and fluoropolymer particles is obtained. This coating is doctored onto a PP spunbonded nonwoven / film laminate and thermally dried / fixed / crosslinked.

FIG. 6 shows a TEM image of the coating with nanosilver. The typically 20 nm large nanosilver particles (black dots in the TEM image) are not aggregated and very uniform in the

Distributed polymer coating. Figure 7 shows the kinetics of killing bacteria

(E.coli.), Which were applied to the coated nonwoven / film laminate. Already after 3.5 hours, 90% of the germs applied are killed. Table 1 shows the result of a microbiological test according to JIS 2801 for the nonwoven / film laminate described. The test uses 2X10⁵ Bacteria placed on the non-woven / foil laminate coated with nanosilver, on an uncoated non-woven / foil laminate and on a standard polystyrene surface. After a cultivation time of 18 hours, the number of living germs is determined. In summary, it can be said that the number of germs on the nanosilver coated fleece / foil laminate compared to

Standard polystyrene can be reduced by 99.8%, while the uncoated fleece / foil laminate is within the

biological fluctuation range shows no germ reduction. The nanosilver coated fleece / foil laminate is considered to have a strong antimicrobial effect.

Table 2 shows the result of the determination of the antimycotic activity of the nanosilver coated nonwoven / film laminate. In summary, it can be stated that the nanosilver coated nonwoven / film laminate shows a significant activity against the 5 fungi tested.

Table 1: Microbiological test according to JIS 2801 for

Nanosilver coated fleece / foil laminate with 150 ppm

1. Test result

<img file="WO2012084072A1_D0001.tif" />

1)% reduction and R-value based on internal standard

JIS Japanese Industrial Standard JIS Z 2801: 2000

Antimicrobial products - Test for antimicrobial activity and efficacy.

- Plate Count Method -

Bacteria test: Escherichia Coli K12

Modification: Sample size: 25 mm x 25 mm

Calculation: R value only

Preincubation C: LB Broth

Preincubation D: LB Broth

Inoculation medium: 1/500 dil. LB Broth (+ 0.13% Tween 80) Incubation: 37 ° C

Sample preparation: UVC sterilizes silver in the coating.

Table 2: Determination of the antimycotic activity for nanosilver coated fleece / foil laminate with 150 ppm silver in the coating.

1. Test result

<img file="WO2012084072A1_D0002.tif" />

2nd Test method SN 195921 - Textile Fabric - Determination of the Antimycotic Activity^■ modified

Test strains: DSM 40464 - Streptomyces abikoensis

DSM 9122 - Scopulariopsis brevicaulis

DSM 62413 - Fusarium solani

DSM 10640 - Penicillium funiculosum

DSM 2404 - Aureobasidium pullulans

Modification: sample size: 30 mm 0

Preincubation: Potato dextrose agar

Suspension medium: Potato dextrose broth

Sample inoculation: spray

Incubation: 25 ° C, humidity chamber

Incubation time: 40 days

Sample sterilization: UVC Example 12:

Use of the formulation according to the invention for

Manufacture of coatings for textile decorative fabrics

The nanosilver dispersion from Example 1 is shown in

Concentrations of 100 mg / kg and 200 mg / kg (based on the silver content in the coating) with the agents of the prior art in a commercial, for

Coating of certain fluoropolymer dispersion incorporated. It becomes a stable, slightly yellow colored dispersion made of nanosilver particles and

Obtained fluoropolymer particles. This coating is applied to a textile decorative fabric and thermally

dried / fixed / cross-linked.

Table 3 shows the results of microbiological tests on doormat decor textiles with 2 different hydrophobic, aqueous coatings and two nanosilver doses according to JIS 1902. The hydrophobic, aqueous coatings AG4 and AG8 are commercially available fluoropolymer coatings. With AG4 coating, a strong reduction in germs compared to an untreated textile is observed with the addition of 100 mg / kg or 200 mg / kg of nanosilver. In the AG8 coating, the addition of 100 mg / kg of nanosilver is not sufficient to prevent the growth of germs. An addition of 200 mg / kg, on the other hand, results in a strong reduction in germs compared to an untreated textile. Table 3: Microbiological tests according to JIS 1902 on doormat decor textiles with 2 different hydrophobic, aqueous coatings and two silver doses each.

1. Test result

<img file="WO2012084072A1_D0003.tif" />

1)% reduction and R-value related to blank

2nd Test method: JIS Japanese Industrial Standard JIS L 1902: 2002 "Testing for antibacterial activity and efficacy on textile products".

- Plate Count Method -

Test strain: Escherichia Coli K12

Modification: weight: 0.4 g

Calculation: R value only

Preincubation C: LB Broth

Preincubation D: LB Broth

Inoculation medium: Phosphate Buffered Saline with 0.05% Tween 80

Incubation: 37 ° C Example 13:

Use of the formulation according to the invention in paints and adhesives

The nanosilver dispersion from Example 1 is incorporated in a concentration of 270 mg / kg (based on the silver content in the finished product), as is known from the prior art, into commercially available paints suitable for painting wood (in particular for sealing stairs and parquet). Stable dispersions with free nanosilver particles are obtained. In Table 4 the results are microbiological

Tests on water-based and solvent-based paints with 270 ppm nanosilver each. In both coatings, an additive of 270 mg / kg nanosilver has a strong effect

Germ reduction compared to the standard surface.

Table 4: Microbiological tests according to JIS 2801 on water and solvent based with 270 ppm nanos each (for sealing stairs and parquet).

1. Test result

<img file="WO2012084072A1_D0004.tif" />

1)% reduction and R-value based on internal standard

2nd Test method: JIS Japanese Industrial Standard JIS Z 2801: 2000

Antimicrabial products - Test for antimicrobial activity and efficacy.

- Plate Count Method -

Test strain: Escherichia Coli K12

Modification: Sample size: 25 mm x 25 mm

Calculation: R value only

Preincubation C: LB Broth

Preincubation D: LB Broth

Inoculate medium: 1/500 dil. LB Broth (+ 0.13% Tween 80)

Incubation: 37 ° C

Sample preparation: UVC sterilized example 14;

Use of the formulation according to the invention in silicones

The nanosilver dispersion from Example 1 is incorporated into commercially available silicones in typical concentrations of 100 mg / kg to 1000 mg / kg (based on the silver content in the finished product), as is known from the prior art. There are stable dispersions with free nanosilver

Receive particles.

Table 5 shows the results of microbiological tests on 2-component silicones with different contents of nanosilver according to JIS 2802. Already one

Additization of 200 mg / kg nanosilver results in a strong germ reduction of 97.5% compared to

Standard surface. From 500 mg / kg nanosilver, a strong germ reduction of 99.9% is achieved.

Table 5: Microbiological tests according to JIS 2801 on 2-component silicones with different contents of nanosilver

1. Test result

<img file="WO2012084072A1_D0005.tif" />

Double determination of independent samples

<img file="WO2012084072A1_D0006.tif" />

1)% reduction and R-value based on internal standard

2nd Test method: JIS Japanese Industrial Standard JIS Z 2801: 2000

Antimicrobial products - Test for antimicrobial activity and efficacy.

- Plate Count Method -

Test strain: Escherichia Co // K12

Modification: Sample size: 25 mm x 25 mm

Calculation: R value only

Preincubation C: LB Broth

Preincubation D: LB Broth

Inoculation medium: 1/500 dil. LB Broth (+0.13% Tween 80) Incubation: 37 ° C

Sample preparation: UVC sterilized Example 15:

Use of the formulation according to the invention in

Polypropylene Films The nanosilver dispersion from Example 1 is incorporated in typical concentrations from 100 mg / kg to 5000 mg / kg (based on the silver content in the finished layer) into a layer of a multilayer polypropylene film by means of extrusion. Films with homogeneously distributed, predominantly isolated nanosilver particles in an approximately 5 μm thick layer are obtained.

Table 6 shows the results of microbiological tests on a multilayer polypropylene film with different contents of nanosilver according to JIS 2801

specified. Additization with 2100 mg / kg or 3200 mg / kg nanosilver results in a strong germ reduction of around 99% compared to the standard surface.

Table 6: Microbiological tests on a multilayer polypropylene film.

1. Test result

<img file="WO2012084072A1_D0007.tif" />

1)% reduction and R value based on internal standard

2. Test method: JIS Japanese Industrial Standard JIS Z 2801: 2000

Antimicrobial products - Test for antimiaobial activity and efficacy.

- Plate Count Method -

Test strain: Escherichia Coli K12

Modification: Sample size: 30 mm x 40 mm

Calculation: R value only

Preincubation: LB medium

Inoculation medium: 1/500 dil. LB Broth (+ 0.13% Tween 80)

Incubation: 37 ° C

Sample preparation: no Example 16:

Use of the formulation according to the invention in

Polypropylene liquor container The nanosilver dispersion from Example 1 is in one

Concentration of 6500 mg / (based on the silver content) incorporated into polypropylene by extrusion. A masterbatch with nanosilver particles that are predominantly isolated from one another is obtained. The nanosilver masterbatch is incorporated into polypropylene liquor containers in typical concentrations of 100 mg / kg to 5000 mg / kg (based on the silver content in the finished polymer). The fleet tanks are used to hold and temporarily store used washing water or Rinsing solutions from dishwashing or textile washing processes determined. The additive of

Nanosilver is said to prevent the polymer from being colonized by germs.

Table 7 shows the results of microbiological tests on polypropylene liquor containers according to JIS 2801 with different contents of nanosilver. The

Additization with 520 mg / kg or 1000 mg / kg or 2000 mg / kg nanosilver results in a strong germ reduction of more than 99.99% compared to the standard surface.

Table 7: Microbiological tests on polypropyl liquor containers according to JIS 2801

1. Test result

<img file="WO2012084072A1_D0008.tif" />

1)% reduction and R value based on internal standard

2nd Test method: JIS Japanese Industrial Standard JIS Z 2801: 2000

Antimicrobial products - Test for antimicrobial activity and efficacy.

- Plate Count Method -

Test strain: Escherichia Coli K12

Modification: Sample size: 30 mm x 40 mm

Calculation: R value only

Preincubation: LB medium

Inoculation medium: 1/500 dil. LB Broth (+0.13% Tween 80)

Incubation: 37 ° C

Sample preparation: no Example 17:

Use of the Formulation According to the Invention in Wood Plastic Composites (WPC) The nanosilver dispersion from Example 1 is used in the

Extrusion of PVC and wood flour mixed in a concentration of 50 mg / kg to 1000 mg / kg. Weather and rot-resistant WPC materials are obtained.

Example 18:

Use of the formulation according to the invention in polyolefin moldings. The nanosilver dispersion from Example 1 is described in

With the help of white oil with polymer beads

Polyolefins (PE or PP) mixed, so that a

Silver concentration of 50 mg / kg to 500 mg / kg in the finished mixture is reached. The mixture is molded in a press (e.g. cutting boards, filters,

Cosmetic applicators) pressed and mechanically

reworked. The resulting cutting boards have antimicrobial activity with an R value between 1 and 4, depending on the silver content.

Example 19:

Use of the formulation according to the invention for

Manufacture of PVC plastisol coated textiles

The nanosilver dispersion from Example 1 is incorporated into PVC plastisol in typical concentrations of 400 mg / kg (based on the silver content in the finished polymer). The plastisol is used to coat textile fabrics. Mats are created that can be used, for example, as flooring in damp rooms, as a gymnastics mat, as a carpet stop or as a dish rack. The addition of nanosilver is intended to prevent the polymer from being colonized by microorganisms.

Table 8 shows the results of microbiological tests on polypropylene liquor containers with a

Additization of 400 mg / kg nanosilver specified. The

Additization with 400 mg / kg nanosilver causes

significant antimycotic activity against the 5th

tested mushrooms.

Table 8: Test for antimycotic activity of PVC

Plastisol with a silver content of 400ppm.

Test result

<img file="WO2012084072A1_D0009.tif" />

Test method SN 195921 - Textile Fabric - Determination of the Antimycotic Activity - modified

Test strains: DSM 40464 - Streptomyces abikoensis

DSM 9122 - Scopulariopsis brevicaulis

DSM 62413 - Fusarium solani

DSM 0640 - Penicillium funiculosum

DSM 2404 - Aureobasidium pullulans

Modification: sample size: 30 mm 0

Preincubation: Potato dextrose agar

Suspension medium: Potato dextrose broth

Sample inoculation: spray

Incubation: 25 ° C

Incubation time: 41 days

Sample sterilization: UVC

Example 20:

Use of the formulation according to the invention in PMMA bone cement The nanosilver dispersion from Example 1 is incorporated into commercially available PMMA bone cements in typical concentrations of 100 mg / kg to 5000 mg / kg (based on the silver content in the finished product) using the agents of the prior art. Incorporation can be done either in the dry PMMA powder or in the liquid MMA monomer. After hardening, bone cements with a homogeneous distribution are predominantly isolated

Obtain nanosilver particles. The results in Table 9 are different

Elution tests indicated.

Table 9 shows that a bone cement equipped with 2149 mg / kg test specimen during an elution with 10 ml SimulatedBodyFluid (SBF) in a

Elution temperature of 37 ° C within 4 days 4 ng silver per mm² Loses area in the solution. It can be seen from the following line in Table 9 that a slight increase in the nanosilver content in the test specimen to 2500 mg / kg and a reduction in the elution time to 5 days does not cause any appreciable change in the amount of silver eluted. In an aging test, an amount of 13 ng / mm was obtained by boiling the test specimen in SBF² eluted. With daily renewal of the elution liquid, an equilibrium of 1.2 ng / mm is established² and day one. Table 9: Acrylate bone cement (PMMA) with 2500 ppm Ag.

<img file="WO2012084072A1_D0010.tif" />

Example 21:

Use of the formulation according to the invention for

Production of PMMA coatings

The nanosilver dispersion from Example 1 is incorporated into commercially available PMMA preparations in typical concentrations of 100 mg / kg to 5000 mg / kg (based on the silver content in the finished product), as is known from the prior art. Incorporation can be done either in the dry PMMA powder or in the liquid MMA monomer. The mixed preparations become

Coating mainly used for medical products. After curing, PMMA coatings with a homogeneous distribution of predominantly isolated nanosilver particles are obtained.

Example 22:

Use of the formulation according to the invention

Production of Synthetic Fibers The nanosilver dispersion from Example 1 is obtained in typical concentrations from 1000 mg / kg to 20,000 mg / kg (based on the silver content) by extrusion into commercially available

Thermoplastics such as polypropylene, polyester, polyamide incorporated. Masterbatches with predominantly isolated nanosilver particles are obtained.

For example, FIG. 8 shows the TEM image of a

Polyester masterbatches with 6500 mg / kg silver. The dark dots in Figure 8 show the homogeneous distribution and the low agglomeration of the nanosilver particles in the polyester.

The masterbatches are diluted according to the state of the art, for example for the production of synthetic fibers

Polypropylene, polyester or polyamide are used.

FIG. 9 shows several microfiber strands made of PET / PA with 200 mg / kg nanosilver. The individual are in FIG

Nanosilver particles (bright spots) clearly visible in the segmented yarns. Typical silver levels for antimicrobial effects are in the range from 100 mg / kg to 300 mg / kg. In addition to microfibers, monofilament and

Bicomponent fibers for clothing, bed fillings, towels and technical textiles as well as nonwoven materials

manufactured. The silver-containing synthetic fibers can also be used in the form of staple fibers for finishing other fibers (including natural fibers such as cotton). The silver contents used are at a higher level compared to the direct finishing of the synthetic fibers, depending on the dilution by other fibers. Figure 10 shows the elution behavior (▲) and

antimicrobial activity (■) of various polyester microfibers. The silver content of the different fibers is in the range from 150 mg / kg to 195 mg / kg. The fibers were each eluted in water for 3 hours. The eluted silver content is in the range from 120 pg / kg to 200 ug kg water; the antimicrobial inhibition is over 96% in each case. Table 10 shows the results of the antimicrobial tests according to JIS 1902 of these 5 microfibers.

Example 23:

Production of a stable dispersion of

Silver nanoparticles in methyl methacrylate

For the preparation of a formulation of

Silver nanoparticles in methyl methacrylate, the product from Example 6 or Example 7 is used. For this purpose, 990 g of methyl methacrylate (Merck, for synthesis) in a 2 L

Beaker submitted and placed on the magnetic stirrer

Room temperature stirred. With a pipette, 1 g

Wetting agent (Evonic, Tego dispers 655) added. After adding 9.3 g of the product from Example 6, the color of the solution changes to orange-brown. By swiveling the glass, a thin film can be generated on the glass wall, which is light yellow, clearly colored and contains no visible particles. 1,000 g of a dispersion are obtained with a silver content of 5,115 mg / kg.

Particle size and distribution correspond to the illustration in FIGS. 2 and 3. Example 24:

Production of a stable dispersion of

Silver nanoparticles in methyl methacrylate For the preparation of a formulation of

Silver nanoparticles in methyl methacrylate, the product from Example 6 or Example 7 is used. For this purpose, 980 g of methyl methacrylate (Merck, for synthesis) in a 2 L

Beaker submitted and placed on the magnetic stirrer

Room temperature stirred. With a pipette, 2 g

Wetting agent (Evonic, Tego dispers 655) added. After the addition of 18.2 g of the product from Example 6, the color of the solution changes to orange-brown. By swiveling the glass, a thin film can be generated on the glass wall, which is light yellow, clearly colored and contains no visible particles. 1,000 g of a dispersion are obtained with a silver content of 10,010 mg / kg.

Particle size and distribution correspond to the illustration in FIGS. 2 and 3.

Example 25:

Production of a stable dispersion of

Silver nanoparticles in methyl methacrylate

For the preparation of a formulation of

Silver nanoparticles in methyl methacrylate, the product from Example 6 or Example 7 is used. For this, 897 g of methyl methacrylate (Merck, for synthesis) in a 2 L

Beaker submitted and placed on the magnetic stirrer

Room temperature stirred. With a pipette, 10 g

Wetting agent (Evonic, Tego dispers 655) added. After the addition of 92.7 g of the product from Example 6, the color of the solution changes to orange-brown. By swiveling the glass, a thin film can be generated on the glass wall, which is light yellow, clearly colored and contains no visible particles. 1,000 g of a dispersion are obtained with a silver content of 50,985 mg / kg.

Particle size and distribution correspond to the illustration in FIGS. 2 and 3.

Example 26:

Manufacture of an antibacterial carrier material based on PMMA

The product from Example 1 is incorporated in a concentration of 100 mg / kg to 10,000 mg / kg, based in each case on the finished product, in a PMMA bead polymer.

It is preferably incorporated into the dry PMMA powder. The PMMA powder can also be another

pharmaceutically active substance such as gentamicin and other additives such as zirconium oxide can be added as an X-ray contrast agent.

The PMMA powder is injection molded

antimicrobial balls, for example with a diameter between 5 and 10 mm and a weight of 100 to 300 mg. It is because of the

Heat resistance of the nanosilver dispersion up to 240 ° C is easily possible. For example, a 200 mg ball may contain 4.5 g gentamicin and 20 mg zirconia.

The balls can be anchored to a multifilament surgical wire.